A photoswitchable polar crystal that exhibits superionic conduction

Nature Chemistry volume 12, pages338–344(2020)Cite this article

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Abstract

Ionic conductors serve as solid electrolytes for fuel cells and batteries, whereas polar crystals such as ferroelectrics and pyroelectrics—which are typically insulating materials—are used in electronic devices. Here we show a material that combines superionic conductivity with a polar crystal structure at room temperature. This three-dimensional anionic network is based on –Fe–N≡C–Mo– units, with Cs cations hosted in every other pore. In the resulting Cs1.1Fe0.95[Mo(CN)5(NO)]·4H2O material, the negative and positive charges of the framework and Cs+ ions, respectively, are non-symmetrically shifted in the c-axis direction of the unit cell, and spontaneous electric polarization is generated, in turn leading to second harmonic generation (SHG). Additionally, this material is a superionic conductor (with an ionic conductivity value of 4 × 10−3 S cm−1 at 318 K). Furthermore, the ionic conductivity significantly decreases under 532 nm light irradiation (from 1 × 10−3 S cm−1 to 6 × 10−5 S cm−1 at room temperature) and, when irradiation stops, returns to its original value within ~1 h.

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Fig. 1: Synthesis and crystal structure of CsFeMo.
Fig. 2: Characterization of the spectroscopic properties of CsFeMo.
Fig. 3: Superionic conductivity in CsFeMo.
Fig. 4: Optical switching of the ionic conductivity of CsFeMo.

Data availability

X-ray crystallographic data have been deposited at the Cambridge Crystallographic Data Centre (http://www.ccdc.cam.ac.uk/) with reference no. 1907012. A copy of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. All other data supporting the findings of this study are available within the Article and its Supplementary Information. Data are also available from the corresponding author upon reasonable request.

References

  1. 1.

    Angell, C. A., Liu, C. & Sanchez, E. Rubbery solid electrolytes with dominant cationic transport and high ambient conductivity. Nature 362, 137–139 (1993).

    CAS  Article  Google Scholar 

  2. 2.

    Tiyapiboonchaiya, C. et al. The zwitterion effect in high-conductivity polyelectrolyte materials. Nat. Mater. 3, 29–32 (2004).

    CAS  PubMed  Article  Google Scholar 

  3. 3.

    Gadjourova, Z., Andreev, Y. G., Tunstall, D. P. & Bruce, P. G. Ionic conductivity in crystalline polymer electrolytes. Nature 412, 520–523 (2001).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  4. 4.

    Makiura, R. et al. Size-controlled stabilization of the superionic phase to room temperature in polymer-coated AgI nanoparticles. Nat. Mater. 8, 476–480 (2009).

    CAS  PubMed  Article  Google Scholar 

  5. 5.

    Kreuer, K. D., Paddison, S. J., Spohr, E. & Schuster, M. Transport in proton conductors for fuel-cell applications: simulations, elementary reactions, and phenomenology. Chem. Rev. 104, 4637–4678 (2004).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  6. 6.

    Croce, F., Appetecchi, G. B., Persi, L. & Scrosati, B. Nanocomposite polymer electrolytes for lithium batteries. Nature 394, 456–458 (1998).

    CAS  Article  Google Scholar 

  7. 7.

    MacFarlane, D. R., Huang, J. & Forsyth, M. Lithium-doped plastic crystal electrolytes exhibiting fast ion conduction for secondary batteries. Nature 402, 792–794 (1999).

    CAS  Article  Google Scholar 

  8. 8.

    Colomban, Ph Proton Conductors: Solids, Membranes and Gels—Materials and Devices (Cambridge Univ. Press, 1992).

  9. 9.

    Mcgeehin, P. & Hooper, A. Fast ion conduction materials. J. Mater. Sci. 12, 1–27 (1977).

    CAS  Article  Google Scholar 

  10. 10.

    Richards, W. D. et al. Design and synthesis of the superionic conductor Na10SnP2S12. Nat. Commun. 7, 11009 (2016).

    CAS  PubMed  PubMed Central  Article  Google Scholar 

  11. 11.

    Hayashi, A., Noi, K. & Tatsumisago, M. Superionic glass–ceramic electrolytes for room-temperature rechargeable sodium batteries. Nat. Commun. 3, 856 (2012).

    PubMed  Article  CAS  PubMed Central  Google Scholar 

  12. 12.

    Kreuer, K.-D., Paddison, S. J., Spohr, E. & Schuster, M. Transport in proton conductors for fuel-cell applications: simulations, elementary reaction, and phenomenology. Chem. Rev. 104, 4637–4678 (2004).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  13. 13.

    Yaghi, O. M. et al. Reticular synthesis and the design of new materials. Nature 423, 705–714 (2003).

    CAS  PubMed  Article  Google Scholar 

  14. 14.

    Kitagawa, S., Kitaura, R. & Noro, S. Functional porous coordination polymers. Angew. Chem. Int. Ed. 43, 2334–2375 (2004).

    CAS  Article  Google Scholar 

  15. 15.

    Ohkoshi, S., Arai, K., Sato, Y. & Hashimoto, K. Humidity-induced magnetization and magnetic pole inversion in a cyano-bridged metal assembly. Nat. Mater. 3, 857–861 (2004).

    CAS  PubMed  Article  Google Scholar 

  16. 16.

    Horike, S., Shimomura, S. & Kitagawa, S. Soft porous crystals. Nat. Chem. 1, 695–704 (2009).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  17. 17.

    Horcajada, P. et al. Porous metal–organic-framework nanoscale carriers as a potential platform for drug delivery and imaging. Nat. Mater. 9, 172–178 (2010).

    CAS  PubMed  Article  Google Scholar 

  18. 18.

    Bogani, L. & Wernsdorfer, W. Molecular spintronics using single-molecule magnets. Nat. Mater. 7, 179–186 (2008).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  19. 19.

    Bureekaew, S. et al. One-dimensional imidazole aggregate in aluminium porous coordination polymers with high proton conductivity. Nat. Mater. 8, 831–836 (2009).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  20. 20.

    Yamada, T., Sadakiyo, M. & Kitagawa, H. High proton conductivity of one-dimensional ferrous oxalate dihydrate. J. Am. Chem. Soc. 131, 3144–3145 (2009).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  21. 21.

    Ohkoshi, S. et al. High proton conductivity in Prussian blue analogs and the interference effect by magnetic ordering. J. Am. Chem. Soc. 132, 6620–6621 (2010).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  22. 22.

    Furukawa, H., Cordova, K. E., O’Keeffe, M. & Yaghi, O. M. The chemistry and applications of metal–organic frameworks. Science 341, 974–986 (2013).

    CAS  Article  Google Scholar 

  23. 23.

    Coronado, E. & Espallargas, G. M. Dynamic magnetic MOFs. Chem. Soc. Rev. 42, 1525–1539 (2013).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  24. 24.

    Pardo, E. et al. High proton conduction in a chiral ferromagnetic metal–organic quartz-like framework. J. Am. Chem. Soc. 133, 15328–15331 (2011).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  25. 25.

    O̅kawa, H. et al. Proton-conductive magnetic metal–organic frameworks, {NR3(CH2COOH)} [Ma IIMb III(ox)3]: effect of carboxyl residue upon proton conduction. J. Am. Chem. Soc. 135, 2256–2262 (2013).

    PubMed  Article  CAS  PubMed Central  Google Scholar 

  26. 26.

    Yang, F. et al. A flexible metal–organic framework with a high density of sulfonic acid sites for proton conduction. Nat. Energy 2, 877–883 (2017).

    CAS  Article  Google Scholar 

  27. 27.

    Feynman, R. P. Slow electrons in a polar crystal. Phys. Rev. 97, 660–665 (1955).

    CAS  Article  Google Scholar 

  28. 28.

    Wang, H. et al. Thermally stable nonlinear optical activity in a smectic-A liquid crystal. Nature 384, 244–247 (1996).

    CAS  Article  Google Scholar 

  29. 29.

    Tayi, A. S. et al. Room-temperature ferroelectricity in supramolecular networks of charge-transfer complexes. Nature 488, 485–489 (2012).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  30. 30.

    Mandal, P. et al. Designing switchable polarization and magnetization at room temperature in an oxide. Nature 525, 363–366 (2015).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  31. 31.

    Pan, R. P., Wei, H. D. & Shen, Y. R. Optical second-harmonic generation from magnetized surfaces. Phys. Rev. B 39, 1229–1234 (1989).

    CAS  Article  Google Scholar 

  32. 32.

    Katz, H. E. et al. Polar orientation of dyes in robust multilayers by zirconium phosphate-phosphonate interlayers. Science 254, 1485–1487 (1991).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  33. 33.

    Chen, C. et al. Design and synthesis of an ultraviolet-transparent nonlinear optical crystal Sr2Be2B2O7. Nature 373, 322–324 (1995).

    CAS  Article  Google Scholar 

  34. 34.

    Berger, V. Nonlinear photonic crystals. Phys. Rev. Lett. 81, 4136–4139 (1998).

    CAS  Article  Google Scholar 

  35. 35.

    Fiebig, M., Lottermoser, Th, Fröhlich, D., Goltsev, A. V. & Pisarev, R. V. Observation of coupled magnetic and electric domains. Nature 419, 818–820 (2002).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  36. 36.

    Campagnola, P. J. & Loew, L. M. Second-harmonic imaging microscopy for visualizing biomolecular arrays in cells, tissues and organisms. Nat. Biotechnol. 21, 1356–1360 (2003).

    CAS  PubMed  Article  Google Scholar 

  37. 37.

    Train, C., Nuida, T., Gheorghe, R., Gruselle, M. & Ohkoshi, S. Large magnetization-induced second harmonic generation in an enantiopure chiral magnet. J. Am. Chem. Soc. 131, 16838–16843 (2009).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  38. 38.

    Ohkoshi, S. et al. 90-degree optical switching of output second harmonic light in chiral photomagnet. Nat. Photon. 8, 65–71 (2014).

    CAS  Article  Google Scholar 

  39. 39.

    Chen, X., Nadiarynkh, O., Plotnikov, S. & Campagnola, P. J. Second harmonic generation microscopy for quantitative analysis of collagen fibrillar structure. Nat. Protoc. 7, 654–669 (2012).

    CAS  PubMed  PubMed Central  Article  Google Scholar 

  40. 40.

    Hsieh, C.-L., Pu, Y., Grange, R., Laporte, G. & Psaltis, D. Imaging with second-harmonic radiation probes in living tissue. Biomed. Opt. Express 2, 2532–2539 (2012).

    Google Scholar 

  41. 41.

    Pantazis, P., Maloney, J., Wu, D. & Fraser, S. E. Second harmonic generating (SHG) nanoprobes for in vivo imaging. Proc. Natl Acad. Sci. USA 107, 14535–14540 (2010).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  42. 42.

    Nakayama, Y. et al. Tunable nanowire nonlinear optical probe. Nature 447, 1098–1102 (2007).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  43. 43.

    Hsieh, C.-L., Grange, R., Pu, Y. & Psaltis, D. Three-dimensional harmonic holographic microcopy using nanoparticles as probes for cell imaging. Opt. Express 17, 2880–2891 (2009).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  44. 44.

    Xuan, L. et al. Photostable second-harmonic generation from a single KTiOPO4 nanocrystal for nonlinear microscopy. Small 4, 1332–1336 (2008).

    Article  CAS  Google Scholar 

  45. 45.

    Delahaye, E. et al. Second harmonic generation from individual hybrid MnPS3-based nanoparticles investigated by nonlinear microscopy. Chem. Phys. Lett. 429, 533–537 (2006).

    CAS  Article  Google Scholar 

  46. 46.

    Bonacina, L. et al. Polar Fe(IO3)3 nanocrystals as local probes for nonlinear microscopy. Appl. Phys. B 87, 399–403 (2007).

    CAS  Article  Google Scholar 

  47. 47.

    Deyneko, D. V. et al. Ferroelectricity, ionic conductivity and structural paths for large cation migration in Ca10.5−xPbx(VO4)7 single crystals, x = 1.9, 3.5, 4.9. CrystEngComm 21, 1309–1319 (2019).

    CAS  Article  Google Scholar 

  48. 48.

    Renz, F. et al. Strong field iron(ii) complex converted by light into a long-lived high-spin state. Angew. Chem. Int. Ed. 39, 3699–3700 (2000).

    CAS  Article  Google Scholar 

  49. 49.

    Ohkoshi, S. et al. Cesium detection by terahertz light. Sci. Rep. 7, 8088 (2017).

    PubMed  PubMed Central  Article  CAS  Google Scholar 

  50. 50.

    Hauser, U., Oestreich, V. & Rohrweck, H. D. On optical dispersion in transparent molecular systems. Z. Phys. A 280, 17–25 (1977).

    CAS  Article  Google Scholar 

  51. 51.

    Coppens, P., Novozhilova, I. & Kovalevsky, A. Photoinduced linkage isomers of transition-metal nitrosyl compounds and related complexes. Chem. Rev. 102, 861–883 (2002).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  52. 52.

    Gütlich, P., Garcia, Y. & Woike, T. Photoswitchable coordination compounds. Coord. Chem. Rev. 219–221, 839–879 (2001).

    Article  Google Scholar 

  53. 53.

    Collet, E. et al. Laser-induced ferroelectric structural order in an organic charge-transfer crystal. Science 300, 612–615 (2003).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  54. 54.

    Margadonna, S., Prassides, K. & Fitch, A. N. Large lattice responses in a mixed-valence prussian blue analogue owing to electronic and spin transitions induced by X-ray irradiation. Angew. Chem. Int. Ed. 43, 6316–6319 (2004).

    CAS  Article  Google Scholar 

  55. 55.

    Polli, D. et al. Coherent orbital waves in the photo-induced insulator–metal dynamics of a magnetoresistive manganite. Nat. Mater. 6, 643–647 (2007).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  56. 56.

    Ohkoshi, S. et al. Synthesis of a metal oxide with a room-temperature photoreversible phase transition. Nat. Chem. 2, 539–545 (2010).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  57. 57.

    Irie, M., Fukaminato, T., Sasaki, T., Tamai, N. & Kawai, T. A digital fluorescent molecular photoswitch. Nature 420, 759–760 (2002).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  58. 58.

    Decurtins, S., Gütlich, P., Köhler, C. P., Spiering, H. & Hauser, A. Light-induced excited spin state trapping in a transition-metal complex: the hexa-1-propyltetrazole-iron(ii) tetrafluoroborate spin-crossover system. Chem. Phys. Lett. 105, 1–4 (1984).

    CAS  Article  Google Scholar 

  59. 59.

    Ohkoshi, S., Imoto, K., Tsunobuchi, Y., Takano, S. & Tokoro, H. Light-induced spin-crossover magnet. Nat. Chem. 3, 564–569 (2011).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  60. 60.

    Heintze, E. et al. Dynamic control of magnetic nanowires by light-induced domain-wall kickoffs. Nat. Mater. 12, 202–206 (2013).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  61. 61.

    Tokoro, H. et al. External stimulation-controllable heat-storage ceramics. Nat. Commun. 6, 7037 (2015).

    CAS  PubMed  PubMed Central  Article  Google Scholar 

  62. 62.

    Bertoni, R. et al. Elastically driven cooperative response of a molecular material impacted by a laser pulse. Nat. Mater. 15, 606–610 (2016).

    CAS  PubMed  Article  PubMed Central  Google Scholar 

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Acknowledgements

The present research was supported partly by a JSPS Grant-in-Aid for Specially Promoted Research (grant 15H05697). We also recognize the Cryogenic Research Center, The University of Tokyo and the Center for Nano Lithography & Analysis, The University of Tokyo, which are supported by MEXT. We thank M. Komura, M. Numanyu and T. Chiba of Olympus Corporation for the SHG microscopy imaging.

Author information

Affiliations

  1. Department of Chemistry, School of Science, The University of Tokyo, Bunkyo-ku, Tokyo, Japan

    Shin-ichi Ohkoshi, Kosuke Nakagawa, Kenta Imoto, Hiroko Tokoro, Yuya Shibata, Kohei Okamoto, Yasuto Miyamoto, Masaya Komine, Marie Yoshikiyo & Asuka Namai

  2. Division of Materials Science, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki, Japan

    Hiroko Tokoro

Authors
  1. Shin-ichi Ohkoshi
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  2. Kosuke Nakagawa
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  3. Kenta Imoto
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  4. Hiroko Tokoro
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Contributions

S.O. designed and coordinated this study, contributed to all measurements and analyses, and wrote the paper. K.N. conducted the conductivity measurements. K.I. conducted the 57Fe Mössbauer spectrum measurements and conductivity measurements. H.T. contributed to the setup of the conductivity measurements and IR measurement systems. Y.S. contributed to the sample characterization, SHG and THz-TDS measurements. K.O. contributed to the sample preparation and TG measurements. Y.M. contributed to the crystal structure analysis. M.K. contributed to the IR measurements. M.Y. contributed to SEM and optical microscopy imaging and partially wrote the paper. A.N. contributed to the analyses of crystal structure and IR spectra, and helped prepare the figures.

Corresponding author

Correspondence to Shin-ichi Ohkoshi.

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The authors declare no competing interests.

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Supplementary information

Supplementary Information

Supplementary Video 1, SEM image and size distribution, crystal structure analysis, terahertz-time domain spectrum, magnetic properties, SHG measurements, photoswitching effect of ionic conductivity, and differential infrared spectra before and after light irradiation.

Crystallographic data

Crystallographic Information File for CsFeMo, CCDC 1907012

Crystallographic data

Structure factors for CsFeMo, CCDC 1907012

Supplementary Video 1

Polar crystal exhibiting a superionic conductivity and optical-switching effect

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Ohkoshi, Si., Nakagawa, K., Imoto, K. et al. A photoswitchable polar crystal that exhibits superionic conduction. Nat. Chem. 12, 338–344 (2020). https://doi.org/10.1038/s41557-020-0427-2

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